Treating hydrocarbon oils



. l 1,628 l532 May 10 1927 w. l.. coun-As; JR

TREATING HYDRcARBoN ons Filed July 12, 1920 Afro/Mfrs Patented May 10, 1927,"A

'UNITED STATES WILLIAM L. contras, Jn.,

O F SEAFORD, NEW YORK.

'rEA'rINe HYDROCARBON oILs.

Apiiation filed vJuly 12,

vThe object of the invention is to provide certain new and useful improvements Lin treating hydrocarbon oils for the production of a water whitehydrocarbonoil of the gasoline series and whichV is of a low boiling point and uniform in quality thus rendering it exceedingly serviceable for use as a motor fuel.

Another object is to permit of treating va-v rieus hydrocarbon oils such as petroleum, fuel oil, gas oil, solar'oil, pressed oil', tar oil and the like. l y

Another object is to render the operation continuous and thereby rendering the process exceedingly efficient, at the same time avoiding the formation of a large percentage.-

of free carbon and uncracked oil.

Another object is to prevent the forma;v tion of carbon in the cracking tubes and the clogging up of the apparatus as is so fre quently -the case in apparatus now used, and

- necessitating periodical stopping of the operations until the defectsy are remedied.

The invention consists essentially iiil a process whereby the hydrocarbon oil is vaporized and then free hydrogen is introduced, while cracking the oil,` to form a vapor of another. hydrocarbon, then distilling such vapor of another.hydrocarbon to separate the vapor of highboiling point from thel vaporof low boiling point, then fractionating the vapor of low boiling point and. filtering the same before and after fractionating, then condensing the vaporsand finally filtering the condensate to form a y water white hydrocarbon oil.

` The process further consists in treating ythevapors of highboiling point the same as the original `hydrocarbon oil, as above set forth.

ln order to-carry -this method intoiedect use ismade of van apparatus shown in the accompanying drawings, in vwhich similarvcharacters of reference indicate corresponding parts in all kthe views.

yFigure 1 is a side elevation of the appa ratuswith parts shown in section;

Figure 2 isan enlarged sectional side ele-V vation of one ofthe filters;

, vFigurek 3 is a similar view of anotherv yfilter. j -1 v.

The apparatus is of multi-stage form and is provided with a number of furnacesllO, 11 and 12 of anyapproved construction and heated in anysuitable manner.v In the up- 1920. Serial No. 395,468.

the coil 19 within the furnace 10. Between .the coils15 and 19 is arranged a water heating pipe 26 with a pump 27 for circulating water through the said coil 25 to heat the same. The outlet end of this coil 25 is connected by a pipe 28 with a steam generating coil .29 arranged in the lower portion ofthe furnace 10. The outlet end of this coil.29 is connected with a'chainber 30 mounted in the furnace'10between the coils 20 and 29. The chamber 30 is connected by ya pipe 31 with the inlet end of'the oil cracking coil 20. The chamber 30 .is charged with a calcium silicon alloy and the steam generated in the.

coil v29 in'passin through the chamber 30 becomes so unsta le that some"oxygen and also some hydrogen lis liberated. The oxycoil 25 connected at its inlet end by a gen readily combines with the permanent gases formed in the cracking reaction while Ithe free h drogen forms with the cracked oil in the coi 2() another vapor of a hydrocarbon and this vapor is delivered by a pipe 35 into a distilling apparatus 36. It is understood that the water delivered by the pump 27 to the coil 25 is subjected in the latter to atemperature'of about 1200 F. generated into steam and superheated, and this superheated steam' is then subjected to a ltemperature o f about 1400 F. in the coil 29. The hydrogen and the oxygen of the generated steam are separated in the chamber 30 andv the free hydrogen combines with the cracked oil at its entrance into the coil 20. It will be noticed that by passing the oil through the coils 15 and 19 and`then throughthe coil 20 it is cracked in two steps, that is', it is first vaporized and superheated during its passage through the coils 15 and 19 and then cracked in the coil 20 while in a vaporized sta-te. As both the oil vapor and the free hydrogen are in ahighly heated'state they readily combine to form another vapor of hydrocarbonespecially as `the ratio yof the hydrogen supplied is not in excess of that required for the desired re-combination.

It is' Well known that the formation df free carbon, in the .form of coke or sludge, in the cracking tubes of the usual apparatus used for cracking oil begins to take place as the vapor produced approaches the outlet. By introducing hydrogen or even highly superheated steam at a point where the hydrocarbons have reached a complete vapor state such' formation of carbon is prevented. These `results are effected and controlled by the .proper rate of oil and water fed and the temperature maintained within the furnace l and that of the cracking oil 20 and the pressure maintained. These conditions vary with different oils and with the various products desired, but by this multi-stage process the cracking action is completed at temperatures safely below the point of decomposition at which end products are formed. It will also be noticed thathigh furnace temperatures are unnecessary when cracking Vin stages.. In the upper portion of the distillingjapparatns 36 are 'arranged filter beds 40 charged with fullers earth or other suitable material. From the top of the dist-illing apparatus rlses a fractionating column 41, provided with a dephlevmator 42 having filter .beds 43, a water jacket 44 and reflux pipes 45 connected with the distilling Aapparatus 36 below the filter beds 40. The vapor en. tering the distilling apparatus 36 has a temratureof about 900 F. and .the sensible eat of the cracked oil is suflicient to distil out the vapors of low boiling point from the f vapors of high boiling point. It will be noticed that the vapor rises from the distilling apparatus 36 and passes into the fractionating column 41 and into' the water-cooled dephlegmator 42 whereby the vapor of high boiling point is condensed and separated from the vapor of low boiling point and returned by the reflux pipes 45 to .the distilling apparatus 36. Theliquid of high boiling point accumulates in the-lower `portion of the distilling apparatus 36 but its level is maintained below the entrance ofthe pipe 35, as shown in Figure 1. The accumulated liquid. of hi h boiling point is for furthery treatment delivered by a piped to a coil 47' contained `in the u per portion of the fur nace 11, as hereina er more fully described.v The liquid accumulated in the lower portiony of the distilling apparatus, 36 remains at a sufiiciently'hightem eratureto assist in distilling out continual y the vapor of low boiling ploint from the vapors continually enter-n ingt e distilling apparatus 36' by the pipe 35.

It will further be noticed that the vaporsf of low boilin point are decolorized and deodoried in .t eir passage through the filter'A lbeds'dSQ-in thedephlegmator 42', and [t f 'va-'porspass from the u per end of the d ph egmator 42h way o a goose'neckll into; g @filter 51' containing filter beds l52 c halrged" iflpwith fullers earth to further dec'olorlz'e andV deordorize the vapors of low boilino point. Any liquid of condensation in the lter 51 passes by way of a refiux pipe 53 to the distilling apparatus 36 while the thoroughly decolorized and deodorized vapor of low boiling point passes from the top of-the filter 51 by wayof a gooseneck 53 into a gas main 54 connected with a condenser 60 in which the vapor is condensed. The result ant condensate flows by its own gravity through a pipe 61, having a pressure relief valve 62, into a filter 63 containing a filter bed 64'to further clarify the condensate. The finished water white or motor fuel flows from the filer 64 by way of a pipe 65 into a tank 66 provided with a valved outlet 67 for drawing off the motor fuel as required. The permanent gases entering the tank 66 with the Water White motor fuel pass by way of a pipe 69 into a gasometer 70 of usual construction.

The above described arrangement `-forms the first Stage of the treatmentyand'the. second sta e begins with the delivery of the liquid o high boiling oint into the coil 4'( contained in the secon furnace 11, as previously mentioned. The'coil y47 is connected by a pipe 80 with a reliminary crack# ing coil 81 connected wit r the cracking coil 82 and into the entranceof this coil passes free hydrogen by 4way of a pipe 83 leading from a chamber 84.- similar to the chamber 30 in the furnace 10. yThe chamber 84 is supplied with Water vapor from a'coil 85 connected by a pipe 86 with a coil 87 connected by a pipe 88 witll a pipe 89 connect ed with the pumpl 27. It is understood that the arrangement ofthe water and oil pipe coils in the furnace 11 'is the same ias above described in reference to the coils inthe fur- Iino los

nace 10 andthe operation is the Same so ythat -90 to 'a distilling apparatus 91 similar to t e distilling apparatus"'36.f and likewise .con-v taining filter beds 92. The distilling a paratus 91 is provided'on the top with a ractionating'columnQS onu which is mounted a dephlegmator 94havin n.lterbed 95, a water -]acket 96' and re ux pipes 97 Vleading back to'thev distilling apparatus 91. action in the distillmg apparatus 91, the fractionating' column 93 and the de hleg-4 mator 9,4is.the4 same as above describe ,that `is, the new vapor is separated into' vaporI` o flowboilingfpoint and vapor of high boiling point, o which: the former passes by way ofjagooseneck 100 into a filterlOl similar tothe filterl and likewise contain-I ing cfil ter. beda `102. A. reflux pipe` 103 -'con-- meets thefuom ofthe. alter. 101 with vthe,

Aapparatus 9 1 a`ndy the upper endv` fof the ter 101 is connected by a' gooseneck "I041wi tltho'gas' main 54 t'o conduct ther The4 ' ing point in the vdistilling apparatus 91 is p ,stage is the same as a n tive toffthe first and second stages so that Leaaeea 101 to the gas main 54 to be condensedin the condenser 60. .The vapor of high boilcondensed and accumulates in the bottom of the distilling apparatus 91 from which it passes by way of a pipe 110 into a coil 111 arranged in the upper portion of the furnace 12.

r1`he third stage is now reached and the liquid passing through the coil 111 passes by way of apipe 112 into and through a preliminary cracking coil 113 connected with a cracking coil 114 supplied with free hydrogen through a pipe 115 -connected with a chamber 116 similar to the chambers 30 and 84 previously described.' The chamber 116 is connected with a decomposing coil 117 connected by a pipe 118 with a coil 119 connected by a water supply pipe 120 with the pipes 8.9 and 26` connected with the pump 27. Ifhe action relative tothe oil and Water in the coil contained in the furnace 12 is the same as above described relative to the furnaces 10 and 11 so that further description of the same is not deemed necessary, itbeing suiiicient to state that the vapor of hydrocarbon formed in the coil 114 passes from the latter by way of a pipe 125 into a distilling apparatus l26similar tothe distilling apparatus 36 and 91.` The distilling apparatus 126 contains filter beds 127 and is vconnected at the top with a fractionating column 128 surmounted by a dephlegmator 129 containing a filter bed 130. Reflux pipes 131 connect the dephlegmator with the distilling apparatus 126. The operation in the distilling apparatus and itsy connected parts is the same as above described, that is, the entering new `vap/or of hydrocarbon is separated into a Vapor of low boiling point and, vapor of high boiling point, of which\ the vapor of low boiling point is conducted by way of a gooseneck 135 into a filter 136 containing filter beds 137. of the filter 136 is connected by a reiuX pipe 138 with the distilling apparatus 126 to return any liquid of condensation from the filter 136 to the `d-istilling apparatus 126. The top of the filter 136 is connected by a gooseneck 139 with the ga's'main 54 to conduct the vapor of low boiling point to the condenser 60. The vapor of high boiling point accumulating in the bottom 0f the distilling apparatus 126 is conducted by a valved pipe 140 into a condensation trap 141 connected by a valved pipe 142 with a separating tank 143 from'which the permanent gas is conductedby a pipe 144 into the gasometer while the liquid in the separating tank is conducted by a valved pipe 145 to a trap 146 having a ,va-lved outlet 147. 'It' is understood that the o eration of the third ve described rela- The lower end Vapor of low lOOliIlgl point from the l'tel 7Vfurther description of the same isy not deemed necessary.

Although 1 have shown and described but three stages, it is evident that for treating some oils two stages may be suiiicient while for treating other oils more than three stages the same as above described may be needed, and hence 1 do not limit myself to the number of stages shown and described.

It will be noticed that the working 'pressure throughout the entire system is equalized or in balance up to the pressure relief valve 62 and the trap 141 and that the product as it leaves the cracking coil 20, 82 or 114 in the several stages is in a vapor state and readily flows upward to the distilling apparatus 36, 91 or 126. The height of'a column of liquid in each of the pipes 46 or 110 is sufficient to provide a head to overcome the pressure of the next stage. By the arrangement described the condensate of high boiling point is compelled to iiow or travel from the distilling apparatus 36 through the pipe 46 into the coil 47 of the second stage. Herein the cracking action is repeated and the vapor is passed to the distillin'g apparatus 91 while the condensate of high boiling point passes by way of the pipe 110 .to the coil 111 of the third stage, from which the new vapor iiows by way of ythe pipe 125 to the distilling apparatus 126 thus completing` the cycle as described above.

The distilling apparatus 36, 91 and -126 may be heated by the waste heat from the furnaces 10, 11 and- 12 or other suitable means. The dephlegmators 42,94 and 129 are water-cooled and the temperature of the vapors of low boiling point passing out of the fractionating columns 41, 93 anti 128 are regulated down to the temperature of the cut. desired.

It is well known that the distillate from a cracked oil can be made water white by redistillation in the presence of fullers earth.) 1n this process it has been found by tests that the Yproduct can be made water white by suspending filter beds arranged in suitable trays located so that only the heated vapors Ifrom the` stills pass through the filter beds,

as will be readily understood by. reference to Fi ures 2 and 3. By this arrangement renewa o f the filtering beds is avoided and the filtering process becomes practically continuous with ythe result that the product is in an exceedingly clarified state. It will banoticed that by the arrangement described a simple, progressive and continuous system of, filtration by easy stages is had whereby \the product is thoroughly decolorized and deodorized thereby producing a water' 'white v motor fuel. It will further be noticed that by the rocess' described a progressive cracking ari distilling is had uninterruptedly in multi-stages under required conditions.

1. A method of treating hydrocarbon oils,

which comprises providing a plurality of furnaces each containing oil-heating coils for the purpose of subjecting the oil passing therethrough to gradually increasing exterior temperatures whereby the oil is treated progressively to the temperature of vaporization, introducing free hydrogen into the oil in the coils of each furnace at the point. Where the oil has reached the vaporization state, said hydrogen being of a temperature of approximately 1400 F., whereby vapors of new hydrocarbons are thus formed, passing the vapors thus produced from each furnace into separate distillation columns, condensing the vapors of high boiling point, fractionating out the vapors of low boiling point in each column, and passing the condensate of high boiling point from each co1- umn to a second furnace for repeating the above steps. i

2. The process of treating hydrocarbon oils which consists 0f passino' the oil through a furnacehaving a series o? coils of gradually increasing temperature which will raise gradually the temperature of the oil until it has reached the vapor point at approximately 5000. F., introducing into the oil vapor free hydrogen at a temperature 0f approxi-` mately 14009 F. to form `ythe vapor of another hydrocarbon, passing the new formed 

